A study of the valence shell electronic states of s-triazine by photoabsorption spectroscopy and ab initio calculations

- The valence shell photoabsorption spectrum of s-triazine has been measured.
- Electronic structure calculated with TDDFT and coupled cluster approaches.
- Assignments proposed for Rydberg and valence states.
- Mixing between Rydberg and valence states important.

The absolute photoabsorption cross section of s-triazine has been measured between 4 and 40 eV, and is dominated by bands associated with valence states. Structure due to Rydberg excitations is both weak and irregular. Jahn-Teller interactions affect the vibronic structure observed in the Rydberg absorption bands due to excitation from the 1e″ or 6e′ orbitals. The interpretation of the experimental spectrum has been guided by transition energies and oscillator strengths, for Rydberg and valence states, calculated with the time-dependent version of density functional theory and with the coupled cluster linear response approach. The theoretical studies indicate that Rydberg/Rydberg and Rydberg/valence mixing is important.

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